Vortex-assisted emulsification semimicroextraction is proposed as a one-step solution-extraction procedure for sample preparation in cosmetic products. The procedure allows rapid preparation based on dispersion of the sample in a mixture of 1 mL of n-hexane and 0.5 mL of ethanol, followed by the addition of 0.5 mL of water and centrifugation to obtain two separated phases. This procedure provides good sample clean-up with minimum dilution and is very useful for the determination of ingredients with restricted concentrations, such as bronopol. The procedure was applied to the determination of bronopol by liquid chromatography with UV detection. The best chromatographic separation was obtained by using a C18 column set at 40 °C and performing a stepwise elution with a mixture of ethanol/aqueous 1 % acetic acid solution as mobile phase pumped at 0.5 mL min−1. The detection wavelength was set at 250 nm and the total run time required was 12 min. The method was successfully applied to 18 commercial cosmetic samples including creams, shampoos, and bath gels. Good recoveries and repeatability were obtained, with a limit of detection of 0.9 μg mL−1, which makes the method suitable for the analytical control of cosmetic products. Moreover, it could be considered environmentally friendly, because water, ethanol, and only a low volume of n-hexane are used as solvents.
This is a preview of subscription content, access via your institution.
Buy single article
Instant access to the full article PDF.
Tax calculation will be finalised during checkout.
Subscribe to journal
Immediate online access to all issues from 2019. Subscription will auto renew annually.
Tax calculation will be finalised during checkout.
Regulation (EC) No. 1233/2009 of the European Parliament and of the Council of 30 November 2009 on cosmetic products. Annexes from III to VII.
Salvador A, Chisvert A. An environmentally friendly (“green”) reversed-phase liquid chromatography method for UV filters determination in cosmetics. Anal Chim Acta. 2005;537:15–24.
Chisvert A, Tarazona I, Salvador A. A reliable and environmentally-friendly liquid-chromatographic method for multi-class determination of fat-soluble UV filters in cosmetic products. Anal Chim Acta. 2013;790:61–7.
Bryce DM, Croshaw B, Hall JE, Holland VR, Lessel B. The activity and safety of the antimicrobial agent bronopol (2-bromo-2-nitropropan-1,3-diol). J Soc Cosmet Chem. 1978;29:3–24.
Shepherd JA, Waigh RD, Gilbert P. Antibacterial action of 2-bromo-2-nitropropane-1,3-diol (bronopol). Antimicrob Agents Chemother. 1988;32:1693–8.
Commission Regulation (EU) No. 358/2014 of 9 April 2014 amending Annexes II and V to Regulation (EC) No. 1233/2009 of the European Parliament and of the Council of 30 November 2009 on cosmetic products.
Matczuk M, Obarski N, Mojski M. The impact of the various chemical and physical factors on the degradation rate of bronopol. Int J Cosmet Sci. 2012;34:451–7.
Kajimura K, Tagami T, Yamamoto T, Iwagami S. The release of formaldehyde upon decomposition of 2-bromo-2-nitropropane-1,3-diol (bronopol). J Health Sci. 2008;54:488–92.
Cui N, Zhang X, Xie Q, Wang S, Chen J, Huang L, et al. Toxicity profile of labile preservative bronopol in water: the role of more persistent and toxic transformation products. Environ Pollut. 2011;159:609–15.
SCCS (Scientific Committee on Consumer Safety) (2012) Opinion on nitrosamines and secondary amines in cosmetic products.
Ferioli V, Vezzalini F, Rustichelli C, Gambernini G. Determination of bronidox and bronopol in cosmetic products by reversed phase high-performance liquid chromatography. Farmaco. 1992;47:833–9.
Hu J, Wang J. Determination of eleven preservatives including bronopol in cosmetic by reversed-phase ion-pair chromatography. Chin J Chromatogr. 1999;17:495–7.
Wang HF, Provan GJ, Helliwell K. Determination of bronopol and its degradation products by HPLC. J Pharm Biomed. 2002;29:387–92.
Marengo E, Gianotti V, Angioi S, Gennaro MC. Optimization by experimental design and artificial neural networks of the ion-interaction reversed-phase liquid chromatographic separation of twenty cosmetic preservatives. J Chromatogr A. 2004;1029:57–65.
Weyland JW, Stern A, Rooselaar J. Determination of bronopol, bronidox and methyldibromo glutaronitrile in cosmetics by liquid chromatography with electrochemical detection. J AOAC Int. 1994;77:1132–6.
Scalia S, Simeoni S, Bousquet E. Determination of bronopol in cosmetic products by HPLC with electrochemical detection. Pharmazie. 2001;56:318–20.
Bendahl L, Hansen SH, Gammergaard B, Sturup S, Nielsen C. Hyphenation of ultra performance liquid chromatography (UPLC) with inductively coupled plasma mass spectrometry (ICP-MS) for fast analysis of bromine containing preservatives. J Pharm Biomed. 2006;40:648–52.
Wu T, Wang C, Wang X, Ma Q. Simultaneous determination of 21 preservatives in cosmetics by ultra performance liquid chromatography. Int J Cosmet Sci. 2006;30:367–72.
Fernandez-Alvarez M, Lamas JP, Sanchez-Prado L, Llompart M, Garcia-Jares C, Lores M. Development of a solid-phase microextraction gas chromatography with microelectron-capture detection method for the determination of 5-bromo-5-nitro-1,3-dioxane in rinse-off cosmetics. J Chromatogr A. 2010;1217:6634–9.
Yiantzi E, Psillakis E, Tyrovola K, Kalogerakis N. Vortex-assisted liquid-liquid microextraction of octylphenol, nonylphenol and bisphenol-A. Talanta. 2010;80:2057–62.
Perez-Serradilla JA, Priego-Capote F, Luque de Castro JA. Simultaneous ultrasound-assisted emulsification–extraction of polar and nonpolar compounds from solid plant samples. Anal Chem. 2007;79:6767–74.
Regueiro J, Llompart M, Garcia-Jares C, Garcia-Monteagudo JC, Cela R. Ultrasound-assisted emulsification-microextraction of emergent contaminants and pesticides in environmental waters. J Chromatogr A. 2008;1190:27–38.
Regueiro J, Llompart M, Psillakis E, Garcia-Monteagudo JC, Garcia-Jares C. Ultrasound-assisted emulsification-microextraction of phenolic preservatives in water. Talanta. 2009;79:1387–97.
Perez-Outeiral J, Millan E, Garcia-Arrona R. Ultrasound-assisted emulsification microextraction coupled with high-performance liquid chromatography for the simultaneous determination of fragrance allergens in cosmetics and water. J Sep Sci. 2015;38:1561–9.
Gonzalez-Hernandez P, Pino V, Ayala JH, Afonso AM. A simplified vortex-assisted emulsification microextraction method for determining personal care products in environmental water samples by ultra-high-performance liquid chromatography. Anal Methods. 2015;7:1825–33.
Jia C, Zhu X, Wang J, Zhao E, He M, Chen L, et al. Extraction of pesticides in water samples using vortex-assisted liquid-liquid microextraction. J Chromatogr A. 2010;1217:5868–71.
Papadopoulou A, Roman IP, Canals A, Tyrovola K, Psillakis E. Fast screening of perfluorooctane sulfonate in water using vortex-assisted liquid-liquid microextraction coupled to liquid chromatography-mass spectrometry. Anal Chim Acta. 2011;691:56–61.
Yang Z, Lu Y, Liu Y, Wu T, Zhou Z, Liu D. Vortex-assisted surfactant-enhanced-emulsification liquid-liquid microextraction. J Chromatogr A. 2011;1218:7071–7.
Moreno-Gonzalez D, Huertas-Perez JF, Garcia-Campana AM, Gamiz-Gracia L. Vortex-assisted surfactant-enhanced emulsification liquid-liquid microextraction for the determination of carbamates in juices by micellar electrokinetic chromatography tandem mass spectrometry. Talanta. 2015;139:174–80.
Leng G, Chen W, Zhang M, Huang F, Cao Q. Determination of phthalate esters in liquor samples by vortex-assisted surfactant-enhanced-emulsification liquid-liquid microextraction followed by GC-MS. J Sep Sci. 2014;37:684–90.
Andruch V, Burdel M, Kocurova L, Sandrejova J, Balogh IS. Application of ultrasonic irradiation and vortex agitation in solvent microextraction. Trends Anal Chem. 2013;49:1–19.
Moradi M, Yamini Y, Ebrahimpour B. Emulsion-based liquid-phase microextraction: a review. J Iran Chem Soc. 2014;11:1087–101.
Spietelun A, Marcinkowski L, de la Guardia M, Namiesnik J. Green aspects, developments and perspectives of liquid phase microextraction techniques. Talanta. 2014;119:34–45.
Miralles P, Chisvert A, Salvador A. Determination of hydroxytyrosol and tyrosol by liquid chromatography for the quality control of cosmetic products based on olive extracts. J Pharm Biomed. 2015;102:157–61.
P.M. would like to thank the Spanish ‘Ministerio de Educación, Cultura y Deporte’ for his predoctoral grant.
We wish to confirm that there are no known conflicts of interest associated with this publication and there has been no financial support for this work that could have influenced its outcome.
About this article
Cite this article
Miralles, P., Bellver, R., Chisvert, A. et al. Vortex-assisted emulsification semimicroextraction for the analytical control of restricted ingredients in cosmetic products: determination of bronopol by liquid chromatography. Anal Bioanal Chem 408, 1929–1934 (2016). https://doi.org/10.1007/s00216-016-9306-5
- Cosmetic products
- Vortex-assisted emulsification
- Liquid chromatography